Decoupling Parasitic Reactions From Bravais Law‐Guided Electroredox Toward Highly Reversible (101)‐Textured Zn Anodes for Ah‐Scale Batteries

ABSTRACT Aqueous Zn–ion batteries (AZIBs) are promising for grid‐scale energy storage but are limited by poor Zn anode reversibility due to dendrite growth and water‐driven parasitic reactions. Although crystallographic texture regulation based on Bravais law can guide Zn plating/stripping, selective facet screening often leaves unprotected facets vulnerable to the parasitic side reactions. This inherent trade‐off in conventional Bravais law‐based texturing strategies leads to unstable and transient texture evolution especially under practical conditions. In this study, we propose a decoupled electrolyte design that simultaneously enables facet‐selective texture control and global suppression of water activity using a formamide (FA) cosolvent and a trace 1‐butyl‐3‐methylimidazolium cation (Bmim + ) additive. Bmim + additive preferentially adsorbs on the Zn(101) facet, retarding its growth and directing Zn plating/stripping toward a (101)‐textured mode, while FA suppresses the bulk/interfacial water activity, thereby suppressing interfacial side reactions on non‐targeted facets. This hierarchical design ensures sustained Zn(101)‐textured electroredox with markedly improved reversibility, delivering 1700 h lifespan in Zn||Zn symmetric cells at 5 mA cm −2 , 5 mAh cm −2 , and 5000 cycles in Zn||I 2 full cells with 79.55% capacity retention at 0.5 A g −1 . Notably, a 1.4 Ah pouch cell further validates the scalability of the proposed decoupling principle for practical AZIBs.